Azo dyes from 6-aminocarbostyrils



United States Patent AZO DYES FROM 6-AM1NOCARBOSTYR1LS Frederick Brody, New York, N. Y., Julian Jacob Leavitt, Somerville, and Robert Sidney Long, Bound Brook, N. J., assignors to American Cyanamid Company, New York, N. Y., a corporation of Maine No Drawing. Application December 23, 1952, Serial No. 327,667

11 Claims. (Cl. 260155) This invention relates to new dyestufis of the azo series and, more specifically, it relates to compounds with the structure O N H in which A stands for the radical of a coupling component, and in which the rings B and C may be further substituted.

In the past it has been ditficult to find new fundamental structures which are easily varied to give a variety of shades of azo dyestufis. Many attempts have been made to find a new class of amino compounds which are easily prepared from readily available and easily substituted intermediates which permit a substituent present and which will give a wide range of shades when coupled onto the usual coupling components. Those that have been found have many times been deficient in dyeing properties such as fastness to light or washing. Since azo dyes have been known for a long time, and since much work has been expended on new amino compounds to be used therein, it is a great contribution to the art to introduce a new class of azo dyes of surprisingly good properties.

Among the many amino compounds which have been used for azo dyes have been numerous heterocyclic compounds. We have now found that the 6-amino derivatives of the carbostyril ring system can be used to prepare azo dyes of remarkable and surprising properties. It was known that this ring system possessed a tautomeric equilibrium:

Because of this, there was no way of predicting in advance what efiect this ring system would have when used in azo dyes. Some of the properties of the parent compound and its classification as a hydroxyquinoline in most textbooks might lead one to expect results analogous to the ordinary amino quinoline. We have found, however, that the properties of the dyes prepared for 6-amino-carbostyrils difier in shadefrom aminoquinoline dyes. We suspect, therefore, that the keto form plays a large role and therefore prefer to represent the formula as a ketone, although we do not wish to be restricted to any theory as to structure.

It is an advantage of the present invention that starting from simple and readily obtainable aromatic amines containing a wide variety of substituents, it is possible to prepare azo dyestuflfs and pigments which exhibit a great variety of shades ranging from yellow to blue and which have good fastness properties to light and washing. It is another advantage of this invention that itis' possible to diazotize these 6-aminocarbostyrils by the normal proce- 2,754,293 Patented July 10, 1956 dure, no special techniques being needed. It is of further advantage that the diazo compounds prepared therefrom couple readily under normal conditions, again needing no special techniques and can be used in any manner in which diazo compounds are norinally used.

The G-aminocarbostyrils can be prepared from simple aromatic amines by straightforward reactions permitting the introduction of substituents as desired. Some of these compounds have been known a long time but have never been used before in azo dyes. The substituents which are presentinthe aromatic amine which is used as the starting material appear in the. final carbostyril attached to the henzene ring (ring B) of the system. The amino group becomes the nitrogen of the heterocyclic ring. Substituents can be introduced into the heterocyclic ring (ring C) by the choice of the reagent used to react with the aromatic amine.

In general, the compounds of the present invention are prepared as follows: the aromatic amine is reacted with an acylacetic ester to give an acylacetarylide.

x l 7 R1 Rel LNH:

(h sO R, f I C 'd cn n5 If the acylacetic ester is ethyl acetoacetate, it may be replaced by diketene R NH:

The acylacetarylides on treatment with sulfuric acid readily ring close to the 4-substituted carbostyrils in which the hydrocarbon part of the acyl group becomes the 4-substituent.

ILSH

joined to form a polymethylene ring.

I i e es r a qa hos yr l unsubst tu d in he 11 h n, e ay start with my a etic. es or hoxv: me h leheacet c est r- T the shhst heh s hich can he in rodu ed. inc ude a s'y .a vl a alk an poly m h l e nd the. bread. scope Qi'the i v ntion o rs. h sih h drqha ad ee s h ch may, of ou e, h further substituted. V

a yr l are h h c n tra e n he, -pes t n, a d i has n f d that Sub titut d. earhhs yt ljs c uta h ng substituents in the benzene ring do' so quite readily; h s by t r wi n a ma ic amine hi h. ha t and 4 P i q eh it s p ssihle t9 chain. the entre- Sponding es bh tyti tq h ch th dyes of. h present invention are prepared; The nitration of these carbostyrils can be illustrated schematically by the following equation in which the R s are hydrogen or substituents to be present in the final carbostyril as indicated:

N l H H The variation of the substituents R4 and R5 by varying the acylacetic ester has already been indicated. To vary the substituents R1, R2 and Ra, it is merely necessary to start with a properly substituted aromatic amine, Thus, to introduce simple. substituentsi such as alkyl, alkpxy, aralkyl, and halogen, one starts with a properly substituted aniline. To introduce an aryl group, one; starts with a diphenyl derivative such as 2-phenylaniline or with another aminodiaryl such as 2-(1- or 2-naphthyl)- aniline, To introd ce. a. ycli e idue. it sneee a yto ta h. a re l/ yclic. i fo e am e a pha: aph v ami e may be eacted. th ace a e iaes e t give the arylide which cyclizes readily as indicatedbelow to give 4-methyl-7,8-benzocarbostyril:

Nnooonzooom usual coupling components for blue azo dyes,

preparation be used as the starting material include o-anisidine, 5- methyl-Lmethoxyaniline, S-ethyl-Z-methoxyaniline, 2,5-. dimethoxyaniline, 2,5-diethoxyaniline, o-phcnetidine, 5- methyl-2-ethoxyaniline, 5-ethyl-2-ethoxyaniline, 5-phenyl-2-methoxyaniline, and the like.

Depending on the nature and position of the substituents in the final base, varying shades are obtainable when these bases are coupled into the usual coupling components. The dyes from the 6-.arninocarbostyrils show a surprising depth of shade, color value, and other fastness properties, when compared with those from isomeric aminocarbostyrils. It is not known why this should be so, and we are unable to explain why dyes from S-aminoand 7-aminocarbostyrils are nowhere nearly as good as those from the 6-aminocarbostyrils.

While a great variety oi shades are obtainable in azo dyes, most of the dyes of this type have shades of yellow, orange, and red. Only a very few aromatic amines are known which give the deeper shades, such as the blues. Commercially, there are only four such blue bases on the market. It is, therefore, a major contribution tov the. art to add another type of structure to the list of amines which will give blue shades. When coupled into the such as the anilides of Z-hydroxy-i-naphthoic acid, the 8-alkoXy-6- aminocarbostyrils give clear, red shades of blue which are not obtainable by the use of the usual blue bases.

It is an advantage of the present invention that the. of such dyestufis does not require special techniques but can be carried out by methods known to theart. The 6-aminocarbostyrils can all be read y diazotized, as will be further described in the examples, and can then be coupled with a wide. variety of coupling components For example, coupling components of the audio type, such as arylides of acetoacetic: acid or 2,- hydroxy-3-naphthoic acid, form insoluble dyestuffs or pigments which can be prepared in bulk. Alternatively, the textiles can be padded with an alkaline, solution of such. an arylide and; treated with the diazo solution to form the insoluble dyestuft on the fiber. It is also possible to, convert the diazo. to a diazoamino compound or other stable derivative for incorporation with a suitable coupling component in an alkaline printing paste, to be applied to goods and followed by acid: development to form the dyestutf on the fiber. Among the azo color coupling components which can be used; for; this purpose are such compounds: as beta-naphthol and derivatives such as 8.-amiuo;2-naphthol, t3raeetylaminQ-Z -naphthol nd. 4-benzoyle ph h pyraz one a dhhyd o ybe zofluorenes and the various N-substituted amides such as arylides of 2-hydroXy-3-naphthoic acid, of 2-hydroxy-3- anthroic acid, of methyl and dirnethyl'salicylic acid, of hydroxycarbazole carboxylic acids, of hydroxybenzocarbazole carboxylic acid, of hydroxybenzacridine carboxylic acid, of hydroxydibenzofuran carboxylic acid, of hydroxydibenzothiophene carboxylic acid, of acetoacetic acid and of befnz'oylacetic acid and the like. The arylidero p n th co pli g componen m y be a imp e are: maticgroup such as the radicalof aniline or of an aniline derivative or of a naphthylamine or it may be the; radical oi a heterooyclic amine such as, for example, an amine; of the. benzothiazole series or of a diamine of the diphenyl sulfone series.

The-am qcarh s yr ls; may also be usedtor th pr par tion of Wa r-sa ab y f u t b e or yeing. getab or. nim l; fibe s-r n; his e a g e t m yof the customary n np ie or: am nic co p g, ompon t may be used. The coupling component, however, must carry a tleast one; sulionic acid group in case the diazo component has none. Illustratiye examples of such cou-- pling components include salicylic acid,r es or cinol, metaphenylenediamine and; aglarge. numberv of naphthol sulfonic acids such as, for example, R-acid, G-acid, Clevesr acid, J-acid, Gamma-acid, I acid urea and I -acid irnide, H-acid and many-others. Byrazolones; such as sultonic acid derivatives of 1-pheny1-3-methylpyrazolone-5 may also be used.

The 6-aminocarbostyrils fluoresce green-blue in ultraviolet light and may be used as intermediates in the manufacture of textile brighteners. These compounds also have antioxidant properties. The invention will be more fully illustrated by the following examples which are meant to be illustrative only and not by way of limitation. All parts are by weight unless otherwise specified.

EXAMPLE 1 2,5-diethoxyacetoacetanilide NH-C O-GHr-C O CH:

602115 A solution of 12 parts of 2,5-diethoxyaniline in 36 parts ethylacetoacetate is boiled under reflux until the condensation is complete. The reaction mixture is cooled and diluted With petroleum ether. The precipitate is then filtered and recrystallized from alcohol.

EXAMPLE 2 5,8-diethoxy-4-methylcarbostyril CsHaO To 184 parts of concentrated sulfuric acid preheated to 85 C. is added 66.4 parts of 2,5-diethoxyacetoacetanilide gradually, keeping the temperature at 83-85 C. The dark brown solution is held at 85-90 C. until the cyclization is complete. It is then cooled and drowned in a mixture of ice and water. The resultant slurry is made basic and filtered, and the product is washed and dried. Recrystallization from aqueous alcohol gives pure 5,8-

diethoxy-4-methylcarbostyril.

EXAMPLE 3 5,8-diet :oxy-4-methyl-6-nitracarbostyril C2115? CH:

0 I N C 2H5 O A cold solution of 5.7 parts of 5,8-diethoxy-4-methylcarbostyril in 31.5 parts of acetic acid is treated dropwise with 2.5 parts of concentrated nitric acid. The resultant slurry is drowned in cold water and filtered. The product is washed acid-free and dried, giving an excellent yield of bright greenish-yellow product.

EXAMPLE 4 6-amin0-5,8-diethoxy-4-methylcarb0styril z s? CH:

A mixture of 6.2 parts of 5,8-diethoxy-4-methyl-6- nitrocarbostyril, 197 parts of alcohol and 0.5 part of palladium-charcoal catalyst is shaken at about 45 C. under hydrogen pressure until the reduction is complete. The catalyst is filtered. The solvent is removed by evaporation and the residual amine is purified by dissolving in dilute hydrochloric acid, clarifying with charcoal, and reprecipitating with ammonia.

EXAMPLE 5 5,8-dimeth0xy-4-methyl-6-nitrocarb0styril CH3 0 (EH;

O N H 0 CH3 5,8 dimethoxy 4 methyl 6 nitrocarbostyril is prepared by treating a cold solution of 4.96 parts of 5,8-dimethoxy-4-methylcarbostyril in 21 parts of acetic acid with 2.1 parts of concentrated nitric acid. The yellow precipitate is filtered, washed with dilute acetic acid and then with water, and dried. The product can be purified by recrystallization from alcohol.

EXAMPLE 6 6-amin0-5,8-dimethoxy-4-methylcarbostyril 0 N (B H CH3 A slurry of 50 parts of 4,5-dimethyl-8-methoxycarbostyril in 525 parts acetic acid and 30 parts 96% nitric acid is stirred and heated on the steam bath until the reaction is complete. The clear red solution is cooled and drowned in water, giving an excellent yield of yellow product which may be further purified by recrystallization from alcohol.

EXAMPLE 8 6-amino-4,S-dimethyl-8-methoxycarbostyril CH3 CH3 CHa A slurry of 3.44 parts of 4,5-dimethyl-8-methoxy-6- nitrocarbostyril in parts alcohol is shaken with palladium-charcoal catalyst under hydrogen pressure with gentle Warming. The greenish slurry is filtered and the product is separated from the catalyst by dissolving in dilute hydrochloric acid, clarifying and reprecipitating '7 8 with ammonia. A small additional amount of amine is shows the complete absence of chlorine andgivesfigures obtained by evaporation of the alcoholic filtrate to dry: for carbon, hydrogen and nitrogen in agfeemfint with the ness. Recrystallization from isopropyl alcohol gives assigned'structure. greenish-yellow needles of the pure amine. 5 I v a EXAMPLE 13 EXAMPLE 9 8-chl0r0-4-methyl-6-nitrocarb0styril fi'mtro4'phenylcarbomnl OzN 0 l I 0m 01 V w. A solution of 11.95 partsof 8-chloro-4-methylcarbo- \N 0 styril in 52.5 parts of acetic acid and 6.0 parts of 96% H nitric acid is boiled under reflux until nitration is complete. It is then cooled and filtered and the product is A solution of 8.0 parts of 4-phenylcarbostyril in 157.5

Washed- AgP yi ld fPa1c yellow product is obtained. parts of acetic acid and 12.0 parts 96% nitric acid is Recrystallization from acetic acid gives the pure nitro tirred at reflux until nitration is complete. On cooling, compound in White needles. the mixture deposits a satisfactory yield of faintly yellow EMMPLE 10 7 Ditto compound. V 6-amino-8-chloro-4-migylcarbostyril EXAMPLE 3 l 6-aminoi-phenylcarbostyril \N O I H Cl A slurry of 7.38 parts of 8-chloro-4-methyl-6-nitrocarbostyril in 120 parts alcohol is hydrogenated over palladium-charcoal catalyst at room temperature. It 0 is then worked up as in Example 8. The product is purified by recrystallization from dichlorobenzene. H

' EXAMPLE 11 A mixture of 3.7 par-ts of 6-nitro-4-pheny1carbostyril, 5-chl0r0-8-meth0xy-4-methyl-fi-nitrocarbostyril 40 P of Palladium-charcoal catalyst, and 200 Parts 01 CBS alcohol is shaken under hydrogen pressure at about 60 C. until the reaction is complete. The catalyst is filtered and ON the yellow-green solution is evaporated to dryness in vacuo. The bright yellow crystalline residue is dissolved 0 in dilute hydrochloric acid. The solution is clarified with N diatomaceous earth and reprecipitated with dilute am- CHQA) H monia, giving anexcellentyield of product, which may To a hot solution of 26.8 parts of 5-chloro-8-methbe crystalhzed from monochlorobenzene' oxy-4-methylcarbostyril in 157 .5 parts acetic acid is added 11.25 parts of 95% nitric acid. The mixture is stirred EXAMPLE 15 and heated on the steam bath until nitration is complete. It is then allowed to cool and filtered. The product is 4 methyl phenylcarbostynl washed acid-free with water, giving agood yield of CH3 bright yellow product which can be recrystallized from I acetic acid.

EXAMPLE 12 6-amin0-8-methoxy-4-meflzylcarb0styril N 0 OH: I

\N O 7 5 H A solution of 20 parts of 2-phenyl-acetoacetanilide 1n 3 110 parts of concentrated sulfuric acid is allowed to stand A slurry of 8.06 parts of 5-chloro-8-methoxy-4-methat room temperature until the ring closure is substantially l-6 i b il i 52.5 parts of acetic acid is treatcomplete. The solution is drowned in 1000 parts water ed with a solution of 27 parts stannous chloride dihydrate and basified with about 150 parts 50% sodium hydroxide. in 41 parts of concentrated hydrochloric acid. The mix- The product is filtered and washed. The filter cake is ture spontaneously heats to the boiling point. After slurried in 300 parts water and 30 parts'20% aqueous cooling, it is drowned in a mixture of 145 parts of 50% sodium hydroxide and stirred overnight. The product is sodium hydroxide and 200 parts of ice. The resultant filtered, washed, and dried at room temperature in vacuo, slurry is filtered, washed alkali-free with water and dried, giving a clear, sticky, pale amber .glass which slowly crysgiving an excellent yield of greenish-yellow product which tallizes on standing, turning to a hard white solid which can be recrystallized from alcohol. Elementary analysis can be recrystallized from aqueous alcohol.

9 EXAMPLE 16 4-methyl-6-nitro-8-phenylcarb0styril A solution of 20.0 parts of 4-methyl-S-phenylcarbostyril in 184 parts of sulfuric acid is chilled to -5 C. and treated with a solution of 7.5 parts of 96% nitric acid in 37 parts concentrated sulfuric acid, holding the temperature at about 5 C. by external cooling. The solution is stirred to room temperature and drowned in water, giving a yellow solid consisting of 4-methyl-6-nitro-8-phenylcarbostyril and 6,X-dinitro-4-methyl 8 phenylcarbostyril, which are separated by fractional crystallization from acetic acid.

EXAMPLE 17 6-amz'no-4-methyl-8-phenylcarbostyril HsN A mixture of 8.3 parts of 4-methyl-6-nitro-8-phenylcarbostyril and 0.5 part of palladium-charcoal catalyst in 80 parts of alcohol is shaken under hydrogen pressure at 40-50 C. until the reaction is complete. After cooling to room temperature, the slurry is filtered. The amine is separated from the catalyst by dissolving in dilute acid, clarifying and reprecipitating with dilute ammonia. The greenish-yellow product can be purified by recrystallization from monochlorobenzene.

EXAMPLE 18 alpha-benzoyl-2,5-diethoxyacetanilia'e A mixture of 8.1 parts of 2,5-diethoxyaniline, 12.9 parts of ethyl benzoylacetate, 83 parts of monochlorobenzene, and 1.5 parts of diethanolamine is refluxed until condensation is complete. The crude product is precipitated with petroleum ether and recrystallized from alcohol to give a satisfactory yield of white needles.

1 0 EXAMPLE 19 5,8-diethoxy-4-phenylcarbostyrii CgHrQ A mixture of 1.0 part of alpha-benzoyl-2,5-diethoxyacetanilide, 1.0 part of para-toluenesulfonic acid monohydrate, and 26.5 parts of benzene is boiled under reflux until cyclization is complete. The benzene is removed by steam distillation and the product filtered from the residual aqueous slurry. It may be recrystallized from butanol. EXAMPLE 20 5,8-diethoxy-6-nitro-4-phenylcarbostyril CzHaO 0 N H 02H:

To a solution of 8.1 parts of 5,8-diethoxy-4-phenylcar bostyril in 26.3 parts of acetic acid is added 3 parts of concentrated nitric acid with stirring and cooling. The mixture is stirred to room temperature and an excellent yield of yellow solid is filtered ofif; the product may be crystallized from dioxane.

EXAMPLE 21 6-amin0-5,8-diethoxy-4-phenylcarb0styril out in excellent yield. Recrystallization from butanol gives bright yellow needles of pure amine.

EXAMPLE 22 7,8-benzo-4-methyl-6-nitrocarbostyril A solution of 10.0 parts 7,8-benzo-4-methylcarbostyril in 262.5 parts acetic acid and 4.5 parts 96% nitric acid is boiled under reflux until no more product separates ,11 from the solution. Filtration gives an excellent yield of yellow product which crystallizes from acetic acid or Cellosolve in bright yellow crystals.

EXAMPLE 23 6-amin0-7,8-benz0-4-methy lcarbstyril HsN V EXAMPLE 24 Z-hydroxy-I (5,8-dieth0xy-4-methylcarbostyrilyl-fi-azo) naphthalene-Swarboxanilide OH N O l l H c o-ryn 0,1350

A slurry of 1.20 parts of 6-amino-5,8-'diethoxy4- methylcarbostyril (Example 4) in 2.5 parts hot Water is treated with 2.4 parts concentrated hydrochloric acid, chilled, treated with parts ice and water and then with a solution of 0.35 part sodium nitrite in 0.35 part water. The slurry dissolves to a clear orange-yellow solution which is clarified with Filter-Cel and diluted with water. The solution is neutralized to the Congo Red endpoint by the addition of sodium acetate solution and then used to dye cotton cloth which has been previously padded with 2% by weight of 2-naphthol-3-carboxanilide. A strong shade of blue is obtained which has good fastness properties. Other anilides oi beta-hydroxy-naphthoic acid give a range of shades varying from red-violet to navy blue.

EXAMPLE 25 N -(4,5 -fimethyl-8-meth oxycarbostyri lyl-6 -azo) N -methylglycine sodium salt "on. on, on.

boom

CHSO

A solution of 20.0 parts 6-amino-4,S-dimethyl-S-rnethoxycarbostyril, 150 parts of water and 42 parts concentrated hydrochloric acid .is cooled to 20 C., diluted with 150 parts of water and diazotized at l9-20 C. with 90 parts N/l sodium nitrite solution. After clarification, the diazo solution is added to an aqueous solution containing 9.55 ,parts methyl glycine sodium salt and 58.4 parts soda ash at 10-15" C. The solution is clarified with one part of activated charcoal and 5 parts diatoinaceous earth, salted to 10% concentration with sodium 'fcliloride and chilled. Filtration gives an excellent yield of stabilized diazo which can be dried in vacuo at 50 C.

A powdered blend is prepared by intimately mixing 4.33 parts of the above stabilized diazo with 3.16 parts 2-naphthol-3-carboxanilide and 2.51 parts of inert diluent, such as dextrin. Three parts of the resultant blend is dissolved in a mixture of 3 parts of 2-ethoxyethanol, 1.25 parts of 30 B. caustic and 22.75 parts water. The solution is stirred into 70 parts of 5% medium viscosity ca'rboxymethylcellulose and the resultant paste is printed on cotton. The cloth is dried, steamed at C. in an atmosphere containing acetic acid, soaped, and dried. The resultant prints are deep violet in shade and show excellent fastness properties.

EXAMPLE 26 The shades of dyes obtained by coupling thediazos of other 6-aminocarbostyril derivatives and various coupling components are shown in the following table:

Amine Component Coupling Component Shade 2-N'aphthol-3-earboxanllide. Bluish-red. Bis-acetoacetotolidide Reddish-yellow. 6-Amino-4-methyl- 4-Chloro-2-hydroxy-3-carba- Yellow-brown.

carbostyril. zole-carboxanilide.

4'-Methoxy-2-naphthol 3 Bordeaux.

earboxanilide. 6-Amin0 -5 S-dimeth- 2-Naphthol-3-earboxanillde Reddish-blue.

ory-4-methylcarbostyril.

2-Naphthol-3-earboxanlllde Navy blue. 2-Methoxy-2-naphthol 3 Deep violet.

i a ri th 13 T lbl 2- y cry-2 -me y -anea ue. ifit g ggifggg thraeenecarboranilide.

Bis-aeetoacetotohdide Golden yellow.

4'-Chloro-2-hydroxy 3 c a r- Red-brown.

bazole-carboxanilide. -Naphthol-3-carboxanillde. Blue. Z-Naphthol-iB-earboxani]ide.. Violet. -Methoxy-2naphthol-3-car- Red-violet. 6-Amino5,8-d1methylboxanilide.

earbostyril. Bis-acetoacetobenzldide. Yellow. 4-Chloro-2-hydroxy 3 c a r- Brown. 7 bazole-carboxanilide. 2-Naphthol'3-carboxanj1ide Violet. 6-Am1no 4,5,8-tr1- 2-Methoxy-2-naphthol 3 Red-violet.

methylcarbostynl. carboxanilide.

2-Naphthol-3-carboxylieacid Red-orange. Bis-aeetoacetotolidide Goldenorange. 2-Naphthol-3-carboxani1ide-. Blue violet. 2-Hydrory-2 methyl-3-an- Blue-violet. 6-Amtno-4,5-dimethylthracenecarboxanilide. Green.

S-methoxycarbo- Bis-acetoacetobenzidide. Yellow. styril. 4'-Ch10ro-2-lrydrory-3-car-' Brown.

bazole-carboxanilide. 2-Naphthol-3-carboxanilide.. Violet. 6-Armno-8-chloro-4- 2-Methoxy-2-naphthol 3 Red-violet.

methylcarbostyril. carboxanilide. Bis-acetoaeetotolidide. .Reddish-yellow. 2-Naphthol-3-carboxtmil i 6 Amin0 8 methoxy 2-Meth yl-2-naphth0l-3-ear Blue-violet.

4-methylcarbostyboxamhdf In Z-Ethoxy-z-naphthol 3 Red-violet.

earboxanilide.

Bis-acetoaeetobenzidide Yellow 2-Naphthol-3-carboxanilide. Red. 2'-Ethoxy-2-naphthol-3-car- Scarlet fi-Amino-t-phenylhoxauilide.

carbostynl. Bis-acetoacetobenzidide Yellow 4-Ohloro-2-liydroxy 3 c a r- Brown bazole-carbox de. 6-Am1no-5,8-d 1eth- 2-Naphthol-3-carboxauilido- Reddish-blue.

oxy-l-phenylcarbostyril.

2-Naphthol-3-carboxanillde Blue. 2-Methoxy-2-naphthol 3 Reddish-blue. 6-A1mn0-7,8-benzo4- earboxanilide.

methylcarbostyril. Bis-acetoaeetotolidide Yellow-brown.

4-Chloro-2-hydroxy 3 c a r- Brown.

bazolecarboxanilide. 2--Methoxy-2naphthol 3 Red.

carboxanilide. 4-'Chloro2 hydroxy 3 ear- Brown. bazolecarboxaniltde. 6-Amlno-4-methyl-8- Bisacetoacetotolidide Yellow.

phenyloarbostyrll. Z-Naghthol-B, -6-.diSull'0nic Deep red.

aci 5, 5'-Dihydroxy-2, 2-dinaph- Reddish-orange.

thyi-ureaJ 7disulfonie 7 our The .8-alk0Xy-6-aminocarhostyrils described above are claimed in copendiug application, Serial No. 406,357, filed January 26, 1954. The .6'amino-7, 8-benzocarbostyrils 13 are claimed in copending application, Serial No. 406,358,

filed January 26, 1954.

in which A is a coupling component; R1 is a member of the group consisting of hydrogen, chlorine, phenyl, lower alkyl and lower alkoxy radicals; R2 and R3 are members of the group consisting of hydrogen, chlorine, phenyl, lower alkyl, lower alkoxy radicals and radicals in which R2 and R3 are joined to form a benzene ring; R; is a member of the group consisting of hydrogen, lower alkyl and phenyl radicals; and R5 is a member of the group consisting of hydrogen, lower alkyl radicals and radicals forming a portion of a cyclohexene ring.

2. A dye of the formula:

in which A is a coupling component.

3. A dye of the formula:

in which A is a coupling component.

4. A dye of the formula:

CH; CH;

in which A is a coupling component.

5. A dye of the formula:

in which A is a coupling component.

6. A dye of the formula:

N=N i in which A is a coupling component.

7. A dye of the formula:

CHaO-QNH-C 5 8. A dye of the formula:

CH3 CH3 0H \N 0 @NH-o CH1!) H 9. A dye of the formula:

O OH; OH \N O MEI-(J30 51 H 10. A dye of the formula:

i1 Qmulo 02H! 11. A dye of the formula:

CzHsO H3 References Cited in the file of this patent UNITED STATES PATENTS 

1. AZO DYES OF THE FORMULA: 